EP1076676B1 - Engineering-ionomerblends und engineering-ionomerblendmembranen - Google Patents
Engineering-ionomerblends und engineering-ionomerblendmembranen Download PDFInfo
- Publication number
- EP1076676B1 EP1076676B1 EP99920761A EP99920761A EP1076676B1 EP 1076676 B1 EP1076676 B1 EP 1076676B1 EP 99920761 A EP99920761 A EP 99920761A EP 99920761 A EP99920761 A EP 99920761A EP 1076676 B1 EP1076676 B1 EP 1076676B1
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- EP
- European Patent Office
- Prior art keywords
- polymer
- acid
- poly
- polymeric
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000012528 membrane Substances 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims description 66
- 229920000642 polymer Polymers 0.000 claims abstract description 69
- 229920002959 polymer blend Polymers 0.000 claims abstract description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 61
- -1 polyethersulphones Polymers 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 18
- 239000000446 fuel Substances 0.000 claims description 17
- 229920005601 base polymer Polymers 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 125000000623 heterocyclic group Chemical group 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000002883 imidazolyl group Chemical group 0.000 claims description 9
- 229920002530 polyetherether ketone Polymers 0.000 claims description 9
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000000010 aprotic solvent Substances 0.000 claims description 7
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 7
- 239000005518 polymer electrolyte Substances 0.000 claims description 7
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 6
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- 150000001734 carboxylic acid salts Chemical class 0.000 claims description 6
- 238000000502 dialysis Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 150000003009 phosphonic acids Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- UGUHFDPGDQDVGX-UHFFFAOYSA-N 1,2,3-thiadiazole Chemical compound C1=CSN=N1 UGUHFDPGDQDVGX-UHFFFAOYSA-N 0.000 claims description 4
- YGTAZGSLCXNBQL-UHFFFAOYSA-N 1,2,4-thiadiazole Chemical compound C=1N=CSN=1 YGTAZGSLCXNBQL-UHFFFAOYSA-N 0.000 claims description 4
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 4
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 claims description 4
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims description 4
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 4
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 claims description 4
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical group C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 claims description 3
- 238000000909 electrodialysis Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 238000005373 pervaporation Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 238000001223 reverse osmosis Methods 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 2
- IIRVGTWONXBBAW-UHFFFAOYSA-M disodium;dioxido(oxo)phosphanium Chemical compound [Na+].[Na+].[O-][P+]([O-])=O IIRVGTWONXBBAW-UHFFFAOYSA-M 0.000 claims description 2
- 238000001728 nano-filtration Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000012078 proton-conducting electrolyte Substances 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 238000000108 ultra-filtration Methods 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical class OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 229910018828 PO3H2 Inorganic materials 0.000 claims 1
- 229920000265 Polyparaphenylene Polymers 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 claims 1
- 229920005597 polymer membrane Polymers 0.000 claims 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims 1
- 150000003568 thioethers Chemical class 0.000 claims 1
- 108091006522 Anion exchangers Proteins 0.000 abstract 1
- 229920002480 polybenzimidazole Polymers 0.000 description 52
- 239000004693 Polybenzimidazole Substances 0.000 description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 229920002492 poly(sulfone) Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 150000003460 sulfonic acids Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000010408 film Substances 0.000 description 6
- 229920000554 ionomer Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 5
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229920006393 polyether sulfone Polymers 0.000 description 4
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical group C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 3
- 229910014276 N-Li Inorganic materials 0.000 description 3
- 229910014326 N—Li Inorganic materials 0.000 description 3
- 238000005349 anion exchange Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005595 deprotonation Effects 0.000 description 3
- 238000010537 deprotonation reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical group C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000012964 benzotriazole Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Chemical group CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Chemical group C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229920003936 perfluorinated ionomer Polymers 0.000 description 2
- 229920000885 poly(2-vinylpyridine) Polymers 0.000 description 2
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 2
- 229920005649 polyetherethersulfone Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 150000003536 tetrazoles Chemical group 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- GEPFDEGNEBYCSR-UHFFFAOYSA-N 1,3-dimethyl-2h-benzimidazole Chemical class C1=CC=C2N(C)CN(C)C2=C1 GEPFDEGNEBYCSR-UHFFFAOYSA-N 0.000 description 1
- RQGURHMTNSNBQX-UHFFFAOYSA-M 1,3-dimethylbenzimidazol-3-ium;iodide Chemical class [I-].C1=CC=C2N(C)C=[N+](C)C2=C1 RQGURHMTNSNBQX-UHFFFAOYSA-M 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- FGYADSCZTQOAFK-UHFFFAOYSA-N 1-methylbenzimidazole Chemical compound C1=CC=C2N(C)C=NC2=C1 FGYADSCZTQOAFK-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical class C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical class C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(c(cc1)ccc1OC)c(cc1)ccc1Oc(cc1S(O)(=O)=O)ccc1S(C(C(C)=CC(C)=C1)C1=*)(=O)=O Chemical compound CC(C)(c(cc1)ccc1OC)c(cc1)ccc1Oc(cc1S(O)(=O)=O)ccc1S(C(C(C)=CC(C)=C1)C1=*)(=O)=O 0.000 description 1
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 206010022528 Interactions Diseases 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000004807 phenyl sulfones Chemical class 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006351 sulfination reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
- B01D71/522—Aromatic polyethers
- B01D71/5222—Polyetherketone, polyetheretherketone, or polyaryletherketone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the invention relates to new compatible binary and ternary Acid-base polymer blends and Acid-base polymer blend membranes.
- the invention further provides the use of these binary and ternary ionomer membranes in electro-membrane processes such as polymer electrolyte membrane fuel cells (PEFC), direct methanol fuel cells (DMFC) and electrodialysis and in other membrane processes such as dialysis and Reverse osmosis, diffusion dialysis, gas permeation, pervaporation and Perstraction.
- PEFC polymer electrolyte membrane fuel cells
- DMFC direct methanol fuel cells
- electrodialysis in other membrane processes such as dialysis and Reverse osmosis, diffusion dialysis, gas permeation, pervaporation and Perstraction.
- PEMFC polymer electrolyte membrane fuel cells
- DMFC direct methanol fuel cells
- PEM-E polymer electrolyte membrane electrolysis
- the perfluorinated ionomer Nafion® (Grot, WG: Perfluorinated Ion Exchange Polymers and Their Use in Research and Industry, Macromolecular Symposia, 82, 161-172 (1994)) meets the high requirements for the chemical, Mechanical and Thermal Stability (Ledjeff, K., Heinzel, A., Mahlendorf, F., Peinecke, V .: The Reversible Membrane Fuel Cell, Dechema Monographs, Volume 128, VCH Verlagsgesellschaft, 103-118 (1993)).
- It has several disadvantages that make the search for alternative materials necessary: It is very expensive (DM 1400 .- / m 2 ).
- the very complex production process contains highly toxic intermediates (see Grot, WG).
- the environmental compatibility of Nafion® has to be critically evaluated: as perfluorinated polymer it is hardly degradable.
- the recyclability of Nafion® is questionable.
- Aryl main chain ion exchange polymers are used as alternative materials for the perfluorinated ionomers such as sulfonated polyethersulfone (Nolte, R .; Ledjeff, K .; Bauer, M .; Mülhaupt, R.: Partially sulfonated poly (arylene ether sulfone) - A Versatile Proton Conducting Membrane Material for Modern Energy Conversion Technologies Journal of Membrane Science 83, 211-220 (1993)) and sulfonated Poly (ether ether ketone) (Helmer-Metzmann, F. Ledjeff, K. Nolte, R., et al. Polymer electrolyte membrane and method for its production EP 0 574 791 A2) in consideration, however, the disadvantage of a high brittleness at dehydration what their application for example in membrane fuel cells unfavorable.
- sulfonated polyethersulfone Nolte,
- polyimides such as the polybenzimidazole PBI poly [(2,2'-m-phenylene) -5,5'-bibenzimidazole] of the general formula: and the polyetherimide poly [2,2'-bis (3,4-dicarboxyphenoxy) phenylpropane-2-phenylene-bisimide] show excellent thermal stabilities (Musto, P., Karasz, FE; MacKnight, WJ: Fourier transform infra-red spectroscopy on the thermooxidative degradation of polybenzimidazole and of a polybenzimidazole / polyetherimide blend, Polymer, 34 (12), 2934-2945 (1993)).
- Process for the preparation of acid-base polymer blends or acid-base polymer blend membranes characterized in that solutions of polymeric sulfonic acids or sulfonic acid salts, polymeric phosphonic acids or phosphonic acid salts and / or polymeric carboxylic acids or carboxylic acid salts and a basic imidazole, benzimidazole and / or others heterocyclic, especially heteroaromatic nitrogen-containing basic groups such as oxazole, isooxazole, carbazole, indole, isoindole, thiazole, isothiazole, benzoxazole, benzothiazole, imidazolidine, indazole, 1,2,3-oxadiazole , 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,3-triazole, benzotriazole, 1,2,4-triazole, tetrazole, pyrrole, pyrrolidine, If necessary, with the addition of LiCl in di
- the invention relates to acid-base polymer blends or Acid-base polymer blend membranes produced by the process according to the invention are available.
- polymeric sulfonic, phosphonic and / or Carboxylic acids or salts used in polymers are selected from polyetheretherketones, polyethersulphones, polyphenylsulphones, Polyphenylene sulfides and / or polyphenylene oxides.
- a polymer is dissolved Sulfonic acid, phosphonic acid and / or carboxylic acid first in one dipolar-aprotic solvent, adds the solution a content of acid groups equivalent amount of a primary, secondary or tertiary amine, then sets a solid or in a dipolar aprotic solvent dissolved basic polymer, the imidazole groups or benzimidazole groups and / or heterocyclic, especially heteroaromatic nitrogen-containing having basic assemblies, and dissolves this polymer also in the solution
- a particular method according to the invention is characterized in that the solution of polymeric sulfonic acid or polymeric sulfonic acid salt, polymeric Phosphonic acid or polymeric phosphonic acid salt, polymeric carboxylic acid or polymeric carboxylic acid salt and imidazole groups or benzimidazole groups and / or other heterocyclic, especially heteroaromatic Nitrogen-containing basic components containing basic polymer according to Claim 1 adds a further polymer, which primary, secondary or tertiary basic nitrogen groups and this polymer in the solution dissolves.
- the polymer blends according to the invention can be used in the form of thin films (membranes) as proton-conducting electrolyte in membrane fuel cells (H 2 polymer electrolyte fuel cells or direct methanol fuel cells), in polymer electrolyte membrane (PEM) electrolysis, in aqueous or nonaqueous electrodialysis or in diffusion dialysis.
- membrane fuel cells H 2 polymer electrolyte fuel cells or direct methanol fuel cells
- PEM polymer electrolyte membrane electrolysis
- aqueous or nonaqueous electrodialysis or in diffusion dialysis in aqueous or nonaqueous electrodialysis or in diffusion dialysis.
- polymer blends according to the invention can be in the form of thinner Films (membranes) or in the form of hollow fibers in pervaporation, perstraction, Gas separation, dialysis, ultrafiltration, nanofiltration or reverse osmosis be used.
- ionic crosslinkers are for the high thermal and mechanical stability of the acid-base blends of the invention responsible.
- the polymer solution was admixed with 10 g of a 15% strength by weight solution of poly (sulfone-ortho) sulfon-diamine) was added in NMP and stirred until homogenization, with this solution a sheet of about 400 ⁇ m thick film was doctored on a glass plate, the solvent was evaporated at a temperature of 120-140 ° C. The glass plate with the thin polymer film became The membrane was dissolved at 60-80 ° C for 24 h in 8% HCl and then for 24 h at temperatures of 20-80 ° C in demineralized water After-treatment with water.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Composite Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Fuel Cell (AREA)
- Conductive Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Materials For Medical Uses (AREA)
- Orthopedics, Nursing, And Contraception (AREA)
- Medicines Containing Plant Substances (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19817374A DE19817374A1 (de) | 1998-04-18 | 1998-04-18 | Engineering-Ionomerblends und Engineering-Ionomermembranen |
| DE19817374 | 1998-04-18 | ||
| PCT/EP1999/002755 WO1999054407A2 (de) | 1998-04-18 | 1999-04-16 | Engineering-ionomerblends und engineering-ionomerblendmembranen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1076676A2 EP1076676A2 (de) | 2001-02-21 |
| EP1076676B1 true EP1076676B1 (de) | 2004-01-28 |
Family
ID=7865050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99920761A Expired - Lifetime EP1076676B1 (de) | 1998-04-18 | 1999-04-16 | Engineering-ionomerblends und engineering-ionomerblendmembranen |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US6723757B1 (da) |
| EP (1) | EP1076676B1 (da) |
| JP (1) | JP3688201B2 (da) |
| KR (1) | KR100586204B1 (da) |
| CN (1) | CN1231538C (da) |
| AT (1) | ATE258570T1 (da) |
| AU (1) | AU769177B2 (da) |
| BR (1) | BR9909720B1 (da) |
| CA (1) | CA2324963C (da) |
| DE (2) | DE19817374A1 (da) |
| DK (1) | DK1076676T3 (da) |
| ES (1) | ES2222031T3 (da) |
| HK (1) | HK1034989A1 (da) |
| IL (2) | IL139051A0 (da) |
| MX (1) | MXPA00010192A (da) |
| MY (1) | MY120071A (da) |
| WO (1) | WO1999054407A2 (da) |
| ZA (1) | ZA200005736B (da) |
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| US6638659B1 (en) * | 1999-04-30 | 2003-10-28 | University Of Connecticut | Membrane electrode assemblies using ionic composite membranes |
| DE19919708A1 (de) * | 1999-04-30 | 2001-03-01 | Univ Stuttgart | Stufenweise Alkylierung von polymeren Aminen |
| GR1003647B (el) * | 1999-12-30 | 2001-08-30 | ����������������������������������������&�������������������...� | Μεμβρανεσαπολυμερωναεμποτισμενεσαμεαοξυαγιααχρησηαωσαστερεοιαηλεκτρολυτεσ.α |
| DE10010001A1 (de) * | 2000-03-02 | 2001-09-06 | Celanese Ventures Gmbh | Neue Blendpolymermembranen zum Einsatz in Brennstoffzellen |
| DE10021106A1 (de) * | 2000-05-02 | 2001-11-08 | Univ Stuttgart | Polymere Membranen |
| CN1439032A (zh) * | 2000-06-02 | 2003-08-27 | Sri国际公司 | 聚合物组合物 |
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| DE10052237A1 (de) | 2000-10-21 | 2002-08-01 | Celanese Ventures Gmbh | Verfahren zur Herstellung einer Lösung von einem Polymer enthaltend wiederkehrende Azoleinheiten, nach dem Verfahren hergestellte Lösungen und deren Verwendung |
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-
1998
- 1998-04-18 DE DE19817374A patent/DE19817374A1/de not_active Withdrawn
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1999
- 1999-04-16 ES ES99920761T patent/ES2222031T3/es not_active Expired - Lifetime
- 1999-04-16 MX MXPA00010192A patent/MXPA00010192A/es active IP Right Grant
- 1999-04-16 EP EP99920761A patent/EP1076676B1/de not_active Expired - Lifetime
- 1999-04-16 BR BRPI9909720-6A patent/BR9909720B1/pt not_active IP Right Cessation
- 1999-04-16 CA CA2324963A patent/CA2324963C/en not_active Expired - Fee Related
- 1999-04-16 AU AU38216/99A patent/AU769177B2/en not_active Expired
- 1999-04-16 KR KR1020007011575A patent/KR100586204B1/ko not_active IP Right Cessation
- 1999-04-16 DE DE59908425T patent/DE59908425D1/de not_active Expired - Lifetime
- 1999-04-16 AT AT99920761T patent/ATE258570T1/de active
- 1999-04-16 JP JP2000544745A patent/JP3688201B2/ja not_active Expired - Lifetime
- 1999-04-16 CN CNB998051748A patent/CN1231538C/zh not_active Expired - Fee Related
- 1999-04-16 DK DK99920761T patent/DK1076676T3/da active
- 1999-04-16 US US09/647,811 patent/US6723757B1/en not_active Expired - Lifetime
- 1999-04-16 WO PCT/EP1999/002755 patent/WO1999054407A2/de active IP Right Grant
- 1999-04-16 IL IL13905199A patent/IL139051A0/xx unknown
- 1999-04-16 MY MYPI99001471A patent/MY120071A/en unknown
-
2000
- 2000-10-16 IL IL139051A patent/IL139051A/en not_active IP Right Cessation
- 2000-10-17 ZA ZA200005736A patent/ZA200005736B/en unknown
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2001
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Also Published As
| Publication number | Publication date |
|---|---|
| AU3821699A (en) | 1999-11-08 |
| MY120071A (en) | 2005-08-30 |
| US6723757B1 (en) | 2004-04-20 |
| BR9909720A (pt) | 2000-12-26 |
| CN1231538C (zh) | 2005-12-14 |
| CA2324963A1 (en) | 1999-10-28 |
| CA2324963C (en) | 2016-06-21 |
| BR9909720B1 (pt) | 2010-09-21 |
| EP1076676A2 (de) | 2001-02-21 |
| AU769177B2 (en) | 2004-01-15 |
| DE19817374A1 (de) | 1999-10-21 |
| IL139051A (en) | 2010-11-30 |
| MXPA00010192A (es) | 2002-08-06 |
| IL139051A0 (en) | 2001-11-25 |
| ZA200005736B (en) | 2002-01-17 |
| ES2222031T3 (es) | 2005-01-16 |
| WO1999054407A2 (de) | 1999-10-28 |
| CN1297467A (zh) | 2001-05-30 |
| JP3688201B2 (ja) | 2005-08-24 |
| HK1034989A1 (en) | 2001-11-09 |
| DK1076676T3 (da) | 2004-06-01 |
| JP2002512291A (ja) | 2002-04-23 |
| KR20010042819A (ko) | 2001-05-25 |
| DE59908425D1 (de) | 2004-03-04 |
| KR100586204B1 (ko) | 2006-06-07 |
| WO1999054407A3 (de) | 2000-03-09 |
| ATE258570T1 (de) | 2004-02-15 |
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